Polymerization of olefins

ABSTRACT

Polyolefins made preferably only from ethylene using a selected ethylene oligomerization catalyst to form α-olefins and a polymerization catalyst which can copolymerize ethylene and α-olefins produces a novel polymer which advantageous rheological properties.

FIELD OF THE INVENTION

[0001] Polymers with varied and useful properties may be produced inprocesses using at least two polymerization catalysts, at least one ofwhich is a selected iron or cobalt catalyst, for the synthesis ofpolyolefins. Novel polymers with improved properties are made using aselected ethylene oligomerization catalyst to form α-olefins and apolymerization catalyst capable of copolymerizing ethylene andα-olefins.

TECHNICAL BACKGROUND

[0002] Polyolefins are most often prepared by polymerization processesin which a transition metal containing catalyst system is used.Depending on the process conditions used and the catalyst system chosen,polymers, even those made from the same monomer(s) may have varyingproperties. Some of the properties which may change are molecular weightand molecular weight distribution, crystallinity, melting point,branching, and glass transition temperature. Except for molecular weightand molecular weight distribution, branching can affect all the otherproperties mentioned.

[0003] It is known that certain transition metal containingpolymerization catalysts containing iron or cobalt, are especiallyuseful in polymerizing ethylene and propylene, see for instance U.S.patent applications Ser. No. 08/991,372, filed Dec. 16, 1997, and09/006,031, filed Jan. 12, 1998 (“equivalents” of World PatentApplications 98/27124 and 98/30612). It is also known that blends ofdistinct polymers, that vary for instance in molecular weight, molecularweight distribution, crystallinity, and/or branching, may haveadvantageous properties compared to “single” polymers. For instance itis known that polymers with broad or bimodal molecular weightdistributions may often be melt processed (be shaped) more easily thannarrower molecular weight distribution polymers. Also, thermoplasticssuch as crystalline polymers may often be toughened by blending withelastomeric polymers.

[0004] Therefore, methods of producing polymers which inherently producepolymer blends are useful especially if a later separate (and expensive)polymer mixing step can be avoided. However in such polymerizations oneshould be aware that two different catalysts may interfere with oneanother, or interact in such a way as to give a single polymer.

[0005] Various reports of “simultaneous” oligomerization andpolymerization of ethylene to form (in most cases) branchedpolyethylenes have appeared in the literature, see for instance WorldPatent Application 90/15085, U.S. Pat. Nos. 5,753,785, 5,856,610,5,686,542, 5,137,994, and 5,071,927, C. Denger, et al,. Makromol. Chem.Rapid Commun., vol. 12, p. 697-701 (1991), and E. A. Benham, et al.,Polymer Engineering and Science, vol. 28, p. 1469-1472 (1988). None ofthese references specifically describes any of the processes herein orany of the branched homopolyethylenes claimed herein.

SUMMARY OF THE INVENTION

[0006] This invention concerns a polyethylene which has one or both of astructural index, S_(T), of about 1.4 or more, and a processabilityindex, P_(R) of about 40 or more, provided that if S_(T) is less thanabout 1.4, said polymer has fewer than 20 methyl branches per 1000methylene groups.

[0007] This invention also concerns a polyethylene which has at least 2branches each of ethyl and n-hexyl or longer and at least one n-butylper 1000 methylene groups, and has fewer than 20 methyl branches per1000 methylene groups, and obeys the equation

[η]<0.0007 Mw^(0.63)

[0008] wherein [η] is the intrinsic viscosity of said polyethylene in1,2,4-trichlorbenzene at 150° C. and Mw is the weight average molecularweight.

BRIEF DESCRIPTION OF THE FIGURES

[0009]FIG. 1 shows the complex viscosity of polyethylenes, versusfrequency of the rheometer, as described in Example 30.

[0010]FIG. 2 shows the intrinsic viscosity, [η], vs. the weight averagemolecular weight, Mw, for a series of polymers of this invention plusvarious other polymers, which are labeled.

DETAILS OF THE INVENTION

[0011] In the polymerization processes and catalyst compositionsdescribed herein certain groups may be present. By hydrocarbyl is meanta univalent radical containing only carbon and hydrogen. By substitutedhydrocarbyl herein is meant a hydrocarbyl group which contains one ormore (types of) substitutents that does not interfere with the operationof the polymerization catalyst system. Suitable substituents in somepolymerizations may include some or all of halo, ester, keto (oxo),amino, imino, carboxyl, phosphite, phosphonite, phosphine, phosphinite,thioether, amide, nitrile, and ether. Preferred substituents are halo,ester, amino, imino, carboxyl, phosphite, phosphonite, phosphine,phosphinite, thioether, and amide. Which substitutents are useful inwhich polymerizations may in some cases be determined by reference toU.S. patent application Ser. Nos. 08/991,372, filed Dec. 16, 1997, and09/006,031, filed Jan. 12, 1998 (and their corresponding World PatentApplications), both of which are hereby included by reference. By anaryl moiety is meant a univalent group whose free valence is to a carbonatom of an aromatic ring. The aryl moiety may contain one or morearomatic ring and may be substituted by inert groups. By phenyl is meantthe C₆H₅-radical, and a phenyl moiety or substituted phenyl is a radicalin which one or more of the hydrogen atoms is replaced by a substituentgroup (which may include hydrocarbyl). Preferred substituents forsubstituted phenyl include those listed above for substitutedhydrocarbyl, plus hydrocarbyl. If not otherwise stated, hydrocarbyl,substituted hydrocarbyl and all other groups containing carbon atoms,such as alkyl, preferably contain 1 to 20 carbon atoms.

[0012] By a polymerization catalyst activator is meant a compound thatreacts with a transition metal compound to form an active polymerizationcatalyst. A preferred polymerization catalyst activator is analkylaluminum compound, that is a compound which has one or more alkylgroups bound to an aluminum atom.

[0013] By a polymerization catalyst component is meant a compositionthat by itself, or after reaction with one or more other compounds(optionally in the presence of the olefins to be polymerized), catalyzesthe polymerization of olefins.

[0014] Noncoordinating ions are mentioned and useful herein. Such anionsare well known to the artisan, see for instance W. Beck., et al., Chem.Rev., vol. 88, p. 1405-1421 (1988), and S. H. Strauss, Chem. Rev., vol.93, p. 927-942 (1993), both of which are hereby included by reference.Relative coordinating abilities of such noncoordinating anions aredescribed in these references, Beck at p. 1411, and Strauss at p. 932,Table III. Useful noncoordinating anions include SbF₆ ⁻, BAF, PF₆ ⁻, orBF₄ ⁻, wherein BAF is tetrakis[3,5-bis(trifluoromethyl)phenyl]borate.

[0015] A neutral Lewis acid or a cationic Lewis or Bronsted acid whosecounterion is a weakly coordinating anion is also present as part of thecatalyst system. By a “neutral Lewis acid” is meant a compound which isa Lewis acid capable of abstracting X from (II) to form a weaklycoordination anion.

[0016] In (II), M is Co or Fe, each X is independently and anion andeach X is such that the total negative charges on X equal the oxidationstate of M. The neutral Lewis acid is originally uncharged (i.e., notionic). Suitable neutral Lewis acids include SbF₅, Ar₃B (wherein Ar isaryl), and BF₃. By a cationic Lewis acid is meant a cation with apositive charge such as Ag⁺, H⁺, and Na⁺.

[0017] In those instances in which (II) does not contain an alkyl orhydride group already bonded to the metal (i.e., X is not alkyl orhydride), the neutral Lewis acid or a cationic Lewis or Bronsted acidalso alkylates or adds a hydride to the metal, i.e., causes an alkylgroup or hydride to become bonded to the metal atom, or a separatecompound is added to add the alkyl or hydride group.

[0018] A preferred neutral Lewis acid, which can alkylate the metal, isa selected alkyl aluminum compound, such as R⁹ ₃Al, R⁹ ₂AlCl, R⁹AlC₂,and “R⁹AlO” (alkylaluminoxanes), wherein R⁹ is alkyl containing 1 to 25carbon atoms, preferably 1 to 4 carbon atoms. Suitable alkyl aluminumcompounds include methylaluminoxane (which is an oligomer with thegeneral formula [MeAlO]_(n)), (C₂H₅)₂AlCl, C₂H₅AlCl₂, and[(CH₃)₂CHCH₂]₃Al. Metal hydrides such as NaBH₄ may be used to bondhydride groups to the metal M.

[0019] For (I) and (II) preferred formulas and compounds are found inU.S. patent application Ser. Nos. 08/991,372, filed Dec. 16, 1997, and09/006,031, filed Jan. 12, 1998, and preferred groupings and compoundsin these applications are also preferred herein. However the compoundnumbers and group (i.e., R^(x)) numbers in these applications may varyfrom those herein, but they are readily convertible. These applicationsalso describe synthesis of (I) and (II).

[0020] There are many different ways of preparing active polymerizationcatalysts from (I) or (II) many of which are described in U.S. patentapplication Ser. Nos. 08/991,372, filed Dec. 16, 1997, and 09/006,031,filed Jan. 12, 1998, and those so described are applicable herein.“Pure” compounds which themselves may be active polymerization catalystsmay be used, or the active polymerization catalyst may be prepared insitu by a variety of methods.

[0021] For instance, olefins may be polymerized by contacting, at atemperature of about −100° C. to about +200° C. a first compound W,which is a neutral Lewis acid capable of abstracting X⁻ to form WX⁻,provided that the anion formed is a weakly coordinating anion; or acationic Lewis or Bronsted acid whose counterion is a weaklycoordinating anion.

[0022] Which first active polymerization catalysts will polymerize whicholefins, and under what conditions, will also be found in U.S. patentapplication Ser. Nos. 08/991,372, filed Dec. 16, 1997, and 09/006,031,filed Jan. 12, 1998. Monomers useful herein for the first activepolymerization catalyst include ethylene and propylene. A preferredmonomer for this catalyst is ethylene.

[0023] In one preferred process described herein the first and secondolefins are identical, and preferred olefins in such a process are thesame as described immediately above. The first and/or second olefins mayalso be a single olefin or a mixture of olefins to make a copolymer.Again it is preferred that they be identical, particularly in a processin which polymerization by the first and second polymerization catalystsmake polymer simultaneously.

[0024] In some processes herein the first active polymerization catalystmay polymerize a monomer that may not be polymerized by said secondactive polymerization catalyst, and/or vice versa. In that instance twochemically distinct polymers may be produced. In another scenario twomonomers would be present, with one polymerization catalyst producing acopolymer, and the other polymerization catalyst producing ahomopolymer, or two copolymers may be produced which vary in the molarproportion or repeat units from the various monomers. Other analogouscombinations will be evident to the artisan.

[0025] In another variation of the process described herein one of thepolymerization catalysts makes an oligomer of an olefin, preferablyethylene, which oligomer has the formula R⁶⁰CH═CH₂, wherein R⁶⁰ isn-alkyl, preferably with an even number of carbon atoms. The otherpolymerization catalyst in the process (co)polymerizes this olefin,either by itself or preferably with at least one other olefin,preferably ethylene, to form a branched polyolefin. Preparation of theoligomer (which is sometimes called an α-olefin) by a first activepolymerization-type of catalyst can be found in U.S. patent application09/005,965, filed Jan. 12, 1998 (“equivalent” of World PatentApplication 99/02472), and B. L. Small, et. al., J. Am. Chem. Soc., vol.120, p. 7143-7144 (1998), all of which are hereby included by reference.These references describe the use of a limited class of compounds suchas (II) to prepare compounds of the formula R⁶⁰ CH═CH₂ from ethylene,and so would qualify as a catalyst that produces this olefin. In apreferred version of this process one of these first-type polymerizationis used to form the α-olefin, and the second active polymerizationcatalyst is a catalyst which is capable of copolymerizing ethylene andolefins of the formula R⁶⁰CH═CH₂, such as a Ziegler-Natta-type ormetallocene-type catalyst. Other types of such catalysts includetransition metal complexes of amidimidates and certain iron or cobaltcomplexes of (I). The amount of branching due to incorporation of theolefin R⁶⁰CH═CH₂ in the polymer can be controlled by the ratio ofα-olefin forming polymerization catalyst to higher polymer formingolefin polymerization catalyst. The higher the proportion of α-olefinforming polymerization catalyst the higher the amount of branching. Thehomopolyethylenes that are made may range from polymers with littlebranching to polymers which contain many branches, that is from highlycrystalline to amorphous homopolyethylenes. In one preferred form,especially when a crystalline polyethylene is being made, the process iscarried out in the gas phase. It is believed that in many cases in gasphase polymerization when both catalysts are present in the sameparticle on which polymerization is taking place (for example originallya supported catalyst), the α-olefin is especially efficiently used(polymerized into the resulting polymer). When amorphous or onlyslightly crystalline homopolyethylenes are being made the process may becarried out in liquid slurry or solution.

[0026] In the variation of the process described in the immediatelypreceding paragraph a novel homopolyethylene is produced. By“homopolyethylene” in this instance is meant a polymer produced in apolymerization in which ethylene is the only polymerizable olefin addedto the polymerization process in a single step, reactor, or bysimultaneous reactions. However it is understood that the polymerproduced is not made by the direct polymerization of ethylene alone, butby the copolymerization of ethylene and α-olefins which are produced insitu. The polymer produced usually contains only branches of the formula(excluding end groups) —(CH₂CH₂)_(n)H wherein n is 1 or more, preferably1 to 100, more preferably 1 to 30, of these branches per 1000 methyleneatoms. Normally there will be branches with a range of “n” in thepolymer. The amount of these branches (as measured by total methylgroups) in the polymer preferably ranges from about 2 to about 200,especially preferably about 5 to about 175, more preferably about 10 toabout 150, and especially preferably about 20 to about 150 branches per1000 methylene groups in the polymer (for the method of measurement andcalculation, see World Patent Application 96/23010). Another preferablerange for these branches is about 50 to about 200 methyl groups per 1000methylene carbon atoms. It is also preferable (either alone or incombination with the other preferable features above) that in thesebranched polymers there is at least 2 branches each of ethyl and n-hexylor longer and at least one n-butyl per 1000 methylene groups, morepreferably at least 4 branches each of ethyl and n-hexyl or longer andat least 2 n-butyl branches per 1000 methylene groups, and especiallypreferably at least 10 branches each of ethyl and n-hexyl or longer andat least 5 n-butyl branches per 1000 methylene groups. It is alsopreferred that there are more ethyl branches than butyl branches in thishomopolyethylene. In another preferred polymer (alone or in combinationwith any of the above preferred features) there is less than 20 methylbranches, more preferably less than 2 methyl branch, and especiallypreferably less than 2 methyl branches (all after correction for endgroups) per 1000 methylene groups.

[0027] In the polymerizations to make the “homopolyethylene” only asingle high molecular weight polymer is produced, that is a polymerwhich has an average degree of polymerization of at least 50, morepreferably at least 200, and especially S preferably at least 400. Thesynthesis of the branched homopolyethylene is believed to be successfulin part because the catalyst which produces the α-olefin often does soat a rate comparable with the polymerization rate, both of them, for thesake of low cost, being relatively rapid.

[0028] These homopolyethylenes also have unusual properties, which givesthem much better processability in processes in which high low shearviscosity and/or low high shear viscose is desirable. For instance, someof the polymers produced by the polymerization herein have unusualrheological properties that make them suitable for the uses describedherein. Using the data shown in FIG. 1, one can calculate certainindices which reflect the improved processing properties. A structuralindex, S_(T), which is defined as

S _(T)=η₀/(8.33×10⁻¹⁴) (M _(w))^(3.4)

[0029] wherein η₀ is the zero shear viscosity at 140° C. and M_(w) isthe weight average molecular weight of the polymer. Materials that havea large proportion of carbon atoms in long chain branches as opposed toshort chain branches will have a relatively high S_(T).Preferably thepolymer used herein have an S_(T) of about 1.4 or more, more preferablyabout 2.0 or more. The S_(T) of various polymers in the Examples isgiven in Table 12, at the end of Example 30.

[0030] Another index which may be used to measure the potential goodprocessability of a polymer, based on its rheological properties, isP_(R), the Processability Index. This is a shear thinning index, and isdefined as

P _(R)=(η* at 0.00628 rad/s)/(η* at 188 rad/s)

[0031] wherein η* is the viscosity at the indicated rate of theviscometer. This is similar to other ratios of vicosities at differentshear levels, but covers a broader range of shears. The higher the valueof P_(R) the greater the shear thinning of the polymer. It is preferredthat P_(R) of the polymers used herein be about 40 or more, morepreferably about 50 or more, and especially preferably about 100 ormore. Furthermore, any combination of S_(T) and P_(R) values mentionedherein are also preferred.

[0032] Another way of finding polymers which may have good rheology (andpossibly long chain branching) is the measuring the Mw versus theintrinsic viscosity. Polymers with good processing characteristics willhave a lower intrinsic viscosity for a given Mw versus a (possibly morelinear) worse processing polymer. FIG. 2 shows such relationshipsbetween various polyethylenes and other similar polymers, some of whichare branched. It is clear that the polymers of this invention have lowerintrinsic viscosities for their Mw's than similar “linear”polyethylenes. The line on the right is fitted to the present invention,while the line on the left is fitted to linear polyethylenes orpolyethylenes with short chain branching only, such as typical LLDPEssuch as Exxon's Exceed®. Indeed for the “better” polymers producedherein one could have the relationship

[η]<0.0007 Mw^(0.66)

[0033] and it is preferred that

[η]<0.0007 Mw^(0.63)

[0034] Of the two lines shown in FIG. 2, the left hand line is of theequation

[η]=0.00054 Mw^(0.69)

[0035] while the right hand line is of the equation

[η]=0.00094 Mw^(0.60)

[0036] For the purposes of these equations, Mw is determined by lightscattering and intrinsic viscosity is determined in1,2,4-trichlorobenzene at 150° C. (see below). The polymers of thepresent invention, especially when they have few methyl groups, andoptionally one or more of the other branching patterns described aboveare thus novel.

[0037] Likewise, conditions for such polymerizations, particularly forcatalysts of the first active polymerization type, will also be found inall of these patent applications. Briefly, the temperature at which thepolymerization is carried out is about −100° C. to about +200° C.,preferably about −20° C. to about +80° C. The polymerization pressurewhich is used with a gaseous olefin is not critical, atmosphericpressure to about 275 MPa, or more, being a suitable range. With aliquid monomer the monomer may be used neat or diluted with anotherliquid (solvent) for the monomer. The ratio of W:(I), when W is present,is preferably about 1 or more, more preferably about 10 or more whenonly W (no other Lewis acid catalyst) is present. These polymerizationsmay be batch, semi-batch or continuous processes, and may be carried outin liquid medium or the gas phase (assuming the monomers have therequisite volatility). These details will also be found in U.S. patentapplications Ser. No. 08/991,372, filed Dec. 16, 1997, and 09/006,031,filed Jan. 12, 1998, and 09/005,965, filed Jan. 12, 1998.

[0038] In these polymerization processes preferred groups for R⁶ is

[0039] wherein:

[0040] R⁸ and R¹³ are each independently hydrocarbyl, substitutedhydrocarbyl or an inert functional group;

[0041] R⁹, R¹⁰, R¹¹, R¹⁴, R¹⁵ and R¹⁶ are each independently hydrogen,hydrocarbyl, substituted hydrocarbyl or an inert functional group;

[0042] R¹² and R¹⁷ are each independently hydrogen, hydrocarbyl,substituted hydrocarbyl or an inert functional group;

[0043] and provided that any two of R⁸, R⁹, R¹⁰, R¹¹, R¹², R¹³, R¹⁴,R¹⁵, R¹⁶ and R¹⁷ that are vicinal to one another, taken together mayform a ring.

[0044] Two chemically different active polymerization catalysts are usedin the polymerization described herein. The first active polymerizationcatalyst is described in detail above. The second active polymerizationcatalyst may also meet the limitations of the first activepolymerization catalyst, but must be chemically distinct. For instance,it may have a different transition metal present, and/or utilize aligand which differs in structure between the first and second activepolymerization catalysts. In one preferred process, the ligand type andthe metal are the same, but the ligands differ in their substituents.

[0045] Included within the definition of two active polymerizationcatalysts are systems in which a single polymerization catalyst is addedtogether with another ligand, preferably the same type of ligand, whichcan displace the original ligand coordinated to the metal of theoriginal active polymerization catalyst, to produce in situ twodifferent polymerization catalysts.

[0046] However other types of catalysts may also be used for the secondactive polymerization catalyst. For instance so-called Ziegler-Nattaand/or metallocene-type catalysts may also be used. These types ofcatalysts are well known in the polyolefin field, see for instanceAngew. Chem., Int. Ed. Engl., vol. 34, p. 1143-1170 (1995), EuropeanPatent Application 416,815 and U.S. Pat. No. 5,198,401 for informationabout metallocene-type catalysts, and J. Boor Jr., Ziegler-NattaCatalysts and Polymerizations, Academic Press, New York, 1979 forinformation about Ziegler-Natta-type catalysts, all of which are herebyincluded by reference. Suitable late metal transition catalysts will befound in World Patent Applications 96/23010 and 97/02298, both of whichare hereby included by reference. Many of the useful polymerizationconditions for these types of catalyst and the first activepolymerization catalysts coincide, so conditions for the polymerizationswith first and second active polymerization catalysts are easilyaccessible. Oftentimes the “co-catalyst” or “activator” is needed formetallocene of Ziegler-Natta-type polymerizations, much as W issometimes needed for polymerizations using the first activepolymerization catalysts. In many instances the same compound, such asan alkylaluminum compound, may be used for these purposes for both typesof polymerization catalysts.

[0047] Suitable catalysts for the second polymerization catalyst alsoinclude metallocene-type catalysts, as described in U.S. Pat. No.5,324,800 and European Patent Application 129,368; particularlyadvantageous are bridged bis-indenyl metallocenes, for instance asdescribed in US Patent 5,145,819 and European Patent Application485,823. Another class of suitable catalysts comprises the well-knownconstrained geometry catalysts, as described in European PatentApplications 416,815, 420,436, 671,404, and 643,066 and World PatentApplication 91/04257. Also the class of transition metal complexesdescribed in WO 96/13529 can be used. Also useful are transition metalcomplexes of bis(carboximidamidatonates), as described in U.S. patentapplication Ser. No. 08/096,668, filed Sep. 1, 1998.

[0048] All the catalysts herein may be “heterogenized” (to form apolymerization catalyst component, for instance) by coating or otherwiseattaching them to solid supports, such as silica or alumina. Where anactive catalyst species is formed by reaction with a compound such as analkylaluminum compound, a support on which the alkylaluminum compound isfirst coated or otherwise attached is contacted with the transitionmetal compounds (or their precursors) to form a catalyst system in whichthe active polymerization catalysts are “attached” to the solid support.These supported catalysts may be used in polymerizations in organicliquids. They may also be used in so-called gas phase polymerizations inwhich the olefin(s) being polymerized are added to the polymerization asgases and no liquid supporting phase is present. The transition metalcompounds-may also be coated onto a support such as a polyolefin(polyethylene, polypropylene, etc.) support, optionally along with otherneeded catalyst components such as one or more alkylaluminum compounds.

[0049] The molar ratio of the first active polymerization catalyst tothe second active polymerization catalyst used will depend on the ratioof polymer from each catalyst desired, and the relative rate ofpolymerization of each catalyst under the process conditions. Forinstance, if one wanted to prepare a “toughened” thermoplasticpolyethylene that contained 80% crystalline polyethylene and 20% rubberypolyethylene, and the rates of polymerization of the two catalysts wereequal, then one would use a 4:1 molar ratio of the catalyst that gavecrystalline polyethylene to the catalyst that gave rubbery polyethylene.More than two active polymerization catalysts may also be used if thedesired product is to contain more than two different types of polymer.

[0050] The polymers made by the first active polymerization catalyst andthe second active polymerization catalyst may be made in sequence, i.e.,a polymerization with one (either first or second) of the catalystsfollowed by a polymerization with the other catalyst, as by using twopolymerization vessels in series. However it is preferred to carry outthe polymerization using the first and second active polymerizationcatalysts in the same vessel(s), i.e., simultaneously. This is possiblebecause in most instances the first and second active polymerizationcatalysts are compatible with each other, and they produce theirdistinctive polymers in the other catalyst's presence.

[0051] The polymers produced by this process may vary in molecularweight and/or molecular weight distribution and/or melting point and/orlevel of crystallinity, and/or glass transition temperature or otherfactors. For copolymers the polymers may differ in ratios of comonomersif the different polymerization catalysts polymerize the monomerspresent at different relative rates. The polymers produced are useful asmolding and extrusion resins and in films as for packaging. They mayhave advantages such as improved melt processing, toughness and improvedlow temperature properties.

[0052] In the Examples, all pressures are gauge pressures.

[0053] In the Examples the transition metal catalysts were eitherbought, or if a vendor is not listed, were made. Synthesis of nickelcontaining catalysts will be found in World Patent Application 96/23010,while synthesis of cobalt and iron containing catalysts will be found inU.S. patent application Ser. Nos. 08/991,372, filed Dec. 16, 1997 and09/006,031, filed Jan. 12, 1998.

[0054] In the Examples PMAO-IP is a form of methylaluminoxane whichstays in solution in toluene, and is commercially available. W440 is aZiegler-Natta type catalyst of unknown structure available from AkzoChemicals, Inc., 1 Livingston Ave., Dobbs Ferry, N.Y. 10522, U.S.A.

EXAMPLES 1-9 AND COMPARATIVE EXAMPLES A-E

[0055] Ethylene Polymerization General Procedure

[0056] The catalyst was weighed into a reaction vessel and was dissolvedin about 20 mL of distilled toluene. The reaction was sealed andtransferred from the drybox to the hood. The reaction was purged withnitrogen, then ethylene. The PMAO-IP (methylaluminoxane solution) wasthen quickly added to the vessel and the reaction was put under 35 kPaethylene. The reaction ran at room temperature in a water bath to helpdissipate heat from any exotherm. The ethylene was then turned off andthe reaction was quenched with about 15 mL of methanol/HCl solution(90/10 volume %) . If polymer was present, the reaction was filtered andthe polymer was rinsed with methanol, then acetone and dried overnightin the hood. The resulting polymer was collected and weighed.

[0057] Below for each polymerization the catalysts used are listed:

EXAMPLE 1

[0058] catalyst 1: 4 mg (0.006 mmol)

[0059] catalyst 2: Zirconocene dichloride, from Strem Chemicals, catalog#93-4002, 2 mg (0.006 mmol)

[0060] co-catalyst: PMAO-IP; 2.0 mmole Al; 1.0 mL of 2.OM in toluene

[0061] duration: 4 h

[0062] polymer: 5.322 g yield

EXAMPLE 2

[0063]

[0064] cocatalyst: PMAO-IP; 2.0 mmol Al; 1.0 mL of 2.0M in toluene

[0065] duration: 4 h

[0066] polymer: 2.282 g yield

EXAMPLE 3

[0067] catalyst 1: 3.5 mg (0.006 mmol)

[0068] catalyst 2: Zirconocene dichloride, from Strem Chemicals, catalog#93-4002, 2 mg (0.006 mmol)

[0069] cocatalyst: PMAO-IP; 2.0 mmol Al; 1.0 mL of 2.0M in toluene

[0070] duration: 4 h

[0071] polymer: 3.651 g yield

EXAMPLE 4

[0072]

[0073] cocatalyst: PMAO-IP; 2.0 mmol Al; 1.0 mL of 2.OM in toluene

[0074] duration: 4 h

[0075] polymer: 2.890 g yield

EXAMPLE 5

[0076]

[0077] cocatalyst: PMAO-IP; 2.0 mmole Al; 1.0 mL of 2.0M in toluene

[0078] duration: 4 h

[0079] polymer: 3.926 g yield

EXAMPLE 6

[0080]

[0081] catalyst 2: W440, from Akzo Nobel, 2.3 wt % Ti, 12 mg (0.006mmole of Ti, based on wt %)

[0082] cocatalyst: PMAO-IP; 2.0 mmole Al; 1.0 mL of 2.0M in toluene

[0083] duration: 4 h

[0084] polymer: 2.643 g yield

EXAMPLE 7

[0085]

[0086] catalyst 2: W440, from Akzo Nobel, 2.3 wt % Ti, 12 mg (0.006mmole of Ti, based on wt %)

[0087] cocatalyst: PMAO-IP; 2.0 mmol Al; 1.0 mL of 2.0M in toluene

[0088] duration: 4 h

[0089] polymer: 2.943 g yield

EXAMPLE 8

[0090]

[0091] catalyst 3: Zirconocene dichloride, from Strem Chemicals, catalog#93-4002, 2 mg (0.006 mmol)

[0092] cocatalyst: PMAO-IP; 3.0 mmol Al; 1.5 mL of 2.0M in toluene

[0093] duration: 4 h

[0094] polymer: 6.178 g yield

EXAMPLE 9

[0095]

[0096] catalyst 3: Zirconocene dichloride, from Strem Chemicals, catalog#93-4002, 2 mg (0.006 mmol)

[0097] cocatalyst: PMAO-IP; 3.0 mmol Al; 1.5 mL of 2.0M in toluene

[0098] duration: 4 h

[0099] polymer: 4.408 g yield

COMPARATIVE EXAMPLE A

[0100] catalyst: Zirconocene dichloride, from Strem Chemicals, catalog#93-4002, 2 mg (0.006 mmol)

[0101] cocatalyst: PMAO-IP; 1.0 mmol Al; 0.5 mL of 2.0M in toluene

[0102] duration: 4 h

[0103] polymer: 2.936 g yield

COMPARATIVE EXAMPLE B

[0104]

[0105] cocatalyst: PMAO-IP; 1.0 mmol Al; 0.5 mL of 2.0M in toluene

[0106] duration: 4 h

[0107] polymer: 1.053 g yield

COMPARATIVE EXAMPLE C

[0108]

[0109] cocatalyst: PMAO-IP; 1.0 mmol Al; 0.5 mL of 2.0M in toluene

[0110] duration: 4 h

[0111] polymer: 2.614 g yield COMPARATIVE EXAMPLE D

[0112] cocatalyst: PMAO-IP; 1.0 mmol Al; 0.5 mL of 2.0M in toluene

[0113] duration: 4 h

[0114] polymer: 2.231 g yield

COMPARATIVE EXAMPLE E

[0115] catalyst: W440, from Akzo Nobel, 2.3 wt % Ti, 12 mg (0.006 mmoleof Ti, based on wt %)

[0116] cocatalyst: PMAO-IP; 1.0 mmol Al; 0.5 mL of 2.0M in toluene

[0117] duration: 4 h

[0118] polymer: 0.326 g yield

EXAMPLES 10-12

[0119] Propylene Polymerization General Procedure

[0120] The catalyst was weighed into a reaction vessel and was dissolvedin about 20 mL of distilled toluene. The reaction was sealed andtransferred from the drybox to the hood. The reaction was purged withnitrogen, then propylene. The MAO was then quickly added to the vesseland the reaction was put under 35 kPa propylene. Reaction ran at 0° C.in an ice bath. The propylene was then turned off and the reaction wasquenched with about 15 mL of methanol/HCl solution (90/10 volume %). Ifpolymer was present, the reaction was filtered and the polymer wasrinsed with methanol, then acetone and dried overnight in the hood. Theresulting polymer was collected and weighed.

EXAMPLE 10

[0121]

[0122] catalyst 2: Zirconocene dichloride, from Strem Chemicals, catalog#93-4002, 2 mg (0.006 mmol)

[0123] cocatalyst: PMAO-IP; 2.0 mmol Al; 1.0 mL of 2.0M in toluene

[0124] duration: 5 h

[0125] polymer: 0.471 g yield

EXAMPLE 11

[0126]

[0127] cocatalyst: PMAO-IP; 2.0 mmole Al; 1.0 mL of 2.0M in toluene

[0128] duration: 5 h

[0129] polymer: 1.191 g yield

EXAMPLE 12

[0130]

[0131] catalyst 2: W440, from Akzo Nobel, 2.3 wt % Ti, 12 mg (0.006mmole of Ti, based on wt %)

[0132] cocatalyst: PMAO-IP; 2.0 mmol Al; 1.0 mL of 2.0M in toluene

[0133] duration: 5 h

[0134] polymer: 0.238 g yield

EXAMPLE 13-17 AND COMPARATIVE EXAMPLES F-N

[0135] In these Examples, compounds A-V and 2 were used as thetransition metal compounds.

[0136] For preparation of: compound A see B. L. Small, et al., J. Am.Chem. Soc., vol. 120, p. 7143-7144(1998); compound B see Ewen, et al.,J. Am. Chem. Soc., vol. 110, p. 6255-6256(1988); compound C see EuropeanPatent Application 416,815; compound D World patent Application98/27124; compound E World patent Application 96/23010; compounds G, H,I and R were purchased from Boulder Scientific company; compounds K, Pand 2 were bought from Strem Chemicals Inc.; compound Q was obtainedfrom Aldrich Chemical Co.; compounds S, T, U and V were made byprocedures described in U.S. patent application Ser. No. 08/096,668,filed Sep. 1, 1998; compound F was made by reacting ZrCl₄ and the amidelithium salt (see J. Chem. Soc., Dalton Trans. 1994, 657) in etherovernight, and removing the ether and pentane extraction gave F 69%yield; compound J was prepared by modifying the procedure of Journal ofOrganometallic Chemistry 1993, 459, 117-123; compounds L and M wereprepared by following the preparation in Macromolecules, 1995, 28,5399-5404, and Journal of Organometallic Chemistry 1994, 472, 113-118;compound N was made by the procedure described in U.S. Pat. No.5,096,867; and compound O was prepared by following a literatureprocedure (Ferdinand R. W. P. Wild, et al., Journal of OrganometallicChemistry 1985, 288, 63-67).

EXAMPLES 13-17 AND COMPARATIVE EXAMPLES F-G

[0137] A 600 mL Parr® reactor was heated up under vacuum and thenallowed to cool under nitrogen. In a drybox, to a Hoke® cylinder wasadded 5mL toluene and a certain amount of PMAO-IP (13.5 wt % toluenesolution) as shown in Table 1. To a 20 mL vial was added the ethylene(co)polymerization catalyst and 2 mL toluene. The solution was thenpipette transferred to a 300 mL RB flask, followed by addition of 150 mL2,2,4-trimethyl pentane. If catalyst A was used, its toluene suspensionwas syringe transferred to the flask. The flask was capped with a rubbersepta. Both the Hoke® cylinder and the flask were brought out of thedrybox. Under nitrogen protection, the transition metal compoundsolution was cannulated to the reactor. The reactor was pressurized withnitrogen and then the nitrogen was released. The reactor was heated to70° C., then, pressurized 2× to 690 kPa ethylene, venting each time andfinally pressurized to 970 kPa with stirring. The MAO solution was addedfrom the Hoke® cylinder at slightly higher pressure. The ethylenepressure of the reactor was then adjusted to the desired pressure (Table1). The reaction mixture was allowed to stir for certain period of time(Table 1). The heating source was removed. Ethylene was vented to about210 kPa. The reactor was back filled with 1.4 MPa nitrogen and was thenvented to 210 kPa. This was repeated once. The reaction mixture was thencooled to RT (room temperature). The reaction mixture was then slowlypoured into 400 mL methanol, followed by addition of 6 mL conc. HCl.Upon stirring at RT for 25 min, polymer was filtered, washed withmethanol six times and dried in vacuo.

EXAMPLES 18-76 (EXCEPT EXAMPLES 22 AND 23) AND COMPARATIVE EXAMPLES H-N

[0138] General procedure for making silica supported catalysts: In adrybox, one of transition metal compounds (but not A), and compound A(0.1 wt % in biphenyl) and silica supported MAO (18 wt % in Al,Albermarle) were mixed with 15 mL of toluene in a 20 mL vial. The vialwas shaken for 45 minutes at RT. The solid was filtered, washed with 3×5mL toluene and dried in- vacuo for 1 hour. It was then stored in afreezer in the drybox and was used the same day.

[0139] General procedure for gas phase ethylene polymerization by thesupported catalysts using a multitube block reactor: In a drybox,supported catalysts (5.0 mg or 2.0 mg each, except Example 20 where 15.0mg was used) were weighed in GC vials. They were placed in a HarperBlock Reactor. The reactor was brought out of the drybox and was chargedwith 1.21 MPa of ethylene. It was then placed in a 90° C. oil bath for 1h under 1.12 MPa of ethylene. The reactor temperature reached 85° C.after 23 minutes and 87° C. after 35 min. The temperature stayed at 87°C. for the rest of the reaction. (Time, temperature and pressure forExamples in Tables 7-9, as noted.) Ethylene was vented. Polymers wereweighed and then submitted for ¹H NMR analysis (TCE-d₂, 120° C.) withoutpurification. Details of these polymerizations are given in Table 2-9.

[0140] In Table 10, the branching distribution [in branches per 1,000methylene (CH₂) groups] of the product polymers of selected examples aregiven. They were determined by ¹³C NMR (TCB, 120° C.). Methods formeasuring the branching distribution are found in World patentApplication 96/23010.

[0141] In all the Tables, where provided, branching levels in thepolymers, Me/1000CH₂ groups, methyl groups per 1000 methylene groups inthe polymer, are measured by the method described in World PatentApplication 96/23010. In the Tables PE is polyethylene, TON is moles ofethylene polymerized/mole of polymerization catalysts (total oftransition metal compounds present)/h, Mn is number average molecularweight, PDI is Mw/Mn where Mw is weight average molecular weight, and Pis ethylene pressure. The PMAO-IP used was 13.5 wt. % in toluene. Theamount of residual α-olefin in the polymer was estimated by ¹H NMR, bymeasurement of the vinylic proton signals of the α-olefin. TABLE 1Catalyst, amount Catalyst A Ex. (×10⁻⁶ (×10⁻⁶ P_(C2H4) Time MMAO PEyield #Me Per m.p. Density(IR) No. mole) mole) MPa T(° C.) (min.) (mL)(g) 1000CH₂ (° C.) Mn/PDI (g/cm³) F B, 8.1 0 1.21  70-100 35 4.2 15.0 1134 43,700/2.2 0.952 13 B, 8.1 0.26 1.31 81-96 25 4.2 24.0 17 116, 10332,400/2.2 0.914 G C, 2.2 0 1.1 90 30 1.2 11.0 4 132 11,700/19.7 0.94014 C, 9.5 0.06 1.31 109-126 30 4.8 31.2 8 133 125,000/2.7 0.937 15 C,9.5 0.13 1.34  80-120 36 4.8 30.0 11 119 68,400/2.5 0.922 16 C, 4.6 0.261.3 71-96 25 2.4 10.3 45 121, 56 94,000/2.3 0.895 261/2.8* 17 C, 3.0 2.31.41 100-116 43 1.5 16.6 52 117, 98 65,000/2.1 0.922 84 214/3.4*

[0142] TABLE 2 Catalyst and PE Ex. amount Catalyst A Al:M:Fe ratio yieldTm No. (×10⁻⁶ mole) (×10⁻⁶ mole) M = Zr, Ti or Fe (g) #Me/1000CH₂ (° C.)Mn/PDI TON H B, 0.033 0 100:1:0 0.195 5 127 24,039/5.2 210,000 I C,0.033 0 1000:1:0 0.075 4 126 125,451/2.1 82,000 18 B, 0.033 0.0011000:1:0.03 0.485 15 120 48,213/4.1 500,000 19 B, 0.033 0.00331000:1:0.1 0.159 62 125 1,916/24.0 150,000 20 C, 0.099 0.00301000:1:0.03 0.200 35 113 63,534/2.7 70,000 21 D, 0.033 0.00171000:1:0.05 0.228 4 133 2,150/26.2 240,000

[0143] TABLE 3 Catalyst Al:M:Fe Catalyst and A ratio PE Ex. amount(X10⁻⁶ M = Zr, yield #Me/ No. (X10⁻⁶ mole) mole) Ti or Fe (g) 1000CH₂TON J H, 0.033 0 1000:1:0 0.421 2 460,000 K I, 0.033 0 1000:1:0 0.135 4150,000 L G, 0.033 0 1000:1:0 0.420 2 460,000 M K, 0.033 0 1000:1:00.091 3  99,000 N R, 0.033 0 1000:1:0 0.203 2 220,000

[0144] TABLE 4 Catalyst and PE α-olefins Ex. amount Catalyst A Al:M:Feratio yield #Me/ Tm left in No. (×10⁻⁶ mole) (×10⁻⁶ mole) M = Zr, Ti orFe (g) 1000CH₂ (° C.) Mn/PDI TON polymer 24 F, 0.033 0.0017 1000:1:0.050.073 66 120 213/18.5 76,000 significant 25 G, 0.033 0.0017 1000:1:0.050.503 13 122, 115 41,525/4.7 520,000 almost none 26 H, 0.033 0.00171000:1:0.05 0.752 9 120, 115 54,825/4.7 780,000 almost none 27 I, 0.0330.0017 1000:1:0.05 0.562 31 119 72,982/3.2 580,000 almost none 28 J,0.033 0.0017 1000:1:0.05 0.032 54 — 895/5.6 33,000 small amount 29 K,0.033 0.0017 1000:1:0.05 0.240 16 123 1,124/16.5 250,000 small amount 30L, 0.033 0.0017 1000:1:0.05 0.112 75 116, 102 — 116,000 significant 31M, 0.033 0.0017 1000:1:0.05 0.092 61 119 — 96,000 significant 32 N,0.033 0.0017 1000:1:0.05 0.068 75 124 485/18.3 71,000 small amount 33 O,0.033 0.0017 1000:1:0.05 0.024 15 — — 25,000 almost none 34 P, 0.0330.0017 1000:1:0.05 0.019 12 — — 20,000 small amount 35 Q, 0.033 0.00171000:1:0.05 0.082 40 — — 85,000 significant 36 2, 0.033 0.00171000:1:0.05 0.157 7 — — 160,000 — 37 R, 0.033 0.0017 1000:1:0.05 0.41610 122 37,993/7.3 450,000 almost none 38 S, 0.033 0.0017 1000:1:0.050.056 59 — — 58,000 significant 39 T, 0.033 0.0017 1000:1:0.05 0.023 73— — 24,000 significant 40 U, 0.033 0.0017 1000:1:0.05 0.102 69 — —110,000 significant 41 V, 0.033 0.0017 1000:1:0.05 0.059 78 — — 61,000significant

[0145] TABLE 5* Catalyst and PE α-olefins Ex. amount Catalyst A Al:M:Feratio Yield #Me/ left in No. (×10⁻⁶ mole) (×10⁻⁶ mole) M = Zr, Ti or Fe(g) 1000CH₂ Mn/PDI TON polymer 42 D, 0.033 0.0033 1000:1:0.10 0.481 83,346/48.6 360,000 significant 43 D, 0.033 0.0082 1000:1:0.25 0.534 14402/156.0 350,000 significant 44 D, 0.033 0.016 1000:1:0.50 0.566 20800/103.0 310,000 significant

[0146] TABLE 6 Catalyst and PE Ex. amount Catalyst A Al:M:Fe ratio yield#Me/ Tm Density No. (×10⁻⁶ mole) (×10⁻⁶ mole) M = Zr, Ti or Fe (g)1000CH₂ (° C.) Mn/PDI TON (g/cm³) 45 H, 0.033 0.0017 1000:1:0.05 0.772 6124 43,791/6.0 800,000 0.930 46 H, 0.013 0.0007 1000:1:0.05 0.367 8 12482,151/3.7 950,000 — 47 I, 0.033 0.0017 1000:1:0.05 0.566 38 11470,462/4.0 590,000 0.909 48 I, 0.013 0.0007 1000:1:0.05 0.226 32 — —590,000 — 49 B, 0.033 0.0010 1000:1:0.03 0.442 8 127 52,673/4.9 460,0000.928 50 B, 0.033 0.0010 1000:1:0.03 0.563 17 120 52,350/4.9 600,000 —51 B, 0.013 0.0004 1000:1:0.03 0.134 16 — — 350,000 — 52 H, 0.033 0.00101000:1:0.03 0.699 — — — 740,000 — 53 N, 0.013 0.0004 1000:1:0.03 0.362 6124 55,102/5.0 960,000 — 54 I, 0.033 0.0010 1000:1:0.03 0.376 15 11898,599/4.0 400,000 — 55 G, 0.033 0.0010 1000:1:0.03 0.665 5 12438,693/6.0 700,000 —

[0147] TABLE 7* Catalyst and PE Ex. amount Catalyst A Al:M:Fe ratioYield #Me/ Tm No. (×10⁻⁶ mole) (×10⁻⁶ mole) M = Zr, Ti or Fe (g) 1000CH₂(° C.) Mn/PDI TON 56 B, 0.033 0.0017 1000:1:0.05 0.740 22 118,10154,734/4.0 380,000 57 B, 0.013 0.0007 1000:1:0.05 0.206 24 — — 270,00058 H, 0.033 0.0017 1000:1:0.05 1.158 7 121 92,063/4.9 600,000 59 H,0.013 0.0007 1000:1:0.05 0.651 12 — — 850,000 60 I, 0.033 0.00171000:1:0.05 0.439 24 102 102,798/3.8 230,000 61 I, 0.013 0.00071000:1:0.05 0.390 25 — — 510,000 62 G, 0.033 0.0017 1000:1:0.05 0.871 9121 45,311/4.7 450,000

[0148] TABLE 8* Catalyst and PE Ex. amount Catalyst A Al:M:Fe ratioyield No. (X10⁻⁶ mole) (X10⁻⁶ mole) M = Zr, Ti or Fe (g) TON 63 B, 0.0130.0007 1000:1:0.05 0.143 370,000 64 B, 0.013 0.0007 1000:1:0.05 0.115300,000 65 H, 0.013 0.0007 1000:1:0.05 0.305 790,000 66 H, 0.013 0.00071000:1:0.05 0.215 560,000 67 I, 0.013 0.0007 1000:1:0.05 0.093 240,00068 I, 0.013 0.0007 1000:1:0.05 0.108 280,000 69 G, 0.013 0.00071000:1:0.05 0.349 900,000

[0149] TABLE 9* Catalyst and PE Ex. amount Catalyst A Al:M:Fe ratioyield #Me/ No. (×10⁻⁶ mole) (×10⁻⁶ mole) M = Zr, Ti or Fe (g) 1000CH₂Mn/PDI TON 70 B, 0.033 0.0017 1000:1:0.05 0.534 37 42,448/3.4 280,000 71B, 0.033 0.0017 1000:1:0.05 0.489 45 — 250,000 72 H, 0.033 0.00171000:1:0.05 0.969 17 77,142/4.8 500,000 73 H, 0.033 0.0017 1000:1:0.051.027 11 — 530,000 74 I, 0.033 0.0017 1000:1:0.05 0.442 34 96,383/4.2230,000 75 I, 0.033 0.0017 1000:1:0.05 0.466 32 — 240,000 76 G, 0.0330.0017 1000:1:0.05 0.710 8 39,693/4.9 370,000

[0150] TABLE 10 Ex. No. Total Me Me Et Pr Bu Am Hex and higher 15 10.5 04.6 0 2.4 0 4.3 13 16 0 6.5 0 3.2 0 6.5 26 59 0 2.9 0 0.4 0 2.5 47 23 08.6 0 4.7 0 10.7 49 8.1 0 3.6 0 1.3 0 3.1

EXAMPLE 22

[0151] In a drybox, 1.7 mg Compound E and 1.0 mg Compound A were mixedwith 40 mL toluene in a Schlenk flask. This was brought out of thedrybox and was purged with ethylene for 15 min at 0° C. MAO toluenesolution (0.64 mL 13.5 wt %) was injected. The mixture was allowed tostir under 0 kPa ethylene at 0° C. for 12 min. Methanol (100 mL) wasinjected, followed by 1 mL conc. HCl. Upon stirring for 25 min at RT,the white solid was filtered, washed with 6×20 mL methanol and dried invacuo. White solid (2.9 g) was obtained. ¹HNMR in TCE-d₂ at 120° C.:44Me/1000CH₂. The polymer contained a significant amount of α-olefins.

EXAMPLE 23

[0152] In a drybox, 30.5 mg of Compound A was mixed with 30.5 g biphenylin a 100 mL Pyrex® glass bottle. This was stirred in a 100° C. bath for25 minutes, during which time Compound A dissolved in biphenyl to form adeep green solution. The solution was allowed to cool down to becomesolid. A 0.1 wt % Compound A/biphenyl homogeneous mixture was obtained.

EXAMPLE 24

[0153] A 600 mL Parr® reactor was heated up under vacuum and thenallowed to cool under nitrogen. In a drybox, to a 300 mL RB flask wasadded 150 mL 2,2,4-trimethylpentane. The flask was capped with a rubberseptum. The flask was brought out of the drybox. Under nitrogenprotection, the 2,2,4-trimethylpentane solvent was cannulated into thereactor. The reactor was pressured up with nitrogen and then nitrogenwas released. This was repeated one more time. The reactor was heated to70° C. Then in a drybox, 160 mg supported catalyst(made by following thegeneral procedure of preparing silica supported catalysts, it contained0.0011 mmole of compound B, 0.000057 mmole compound A and 1.1 mmole ofMAO) was mixed with 4 mL cyclohexane and was transferred to a 5 mL gastight syringe with long needle. This was brought out of the drybox andwas injected into the reactor under nitrogen protection (positivenitrogen pressure). The reactor was pressured up with 1.2 MPa ofnitrogen, then released to 14 kPa. This was repeated one more time.Under stirring, the reactor was pressured up with ethylene to 1.2 MPa.The reaction mixture was allowed to stir at between 70° C. to 97° C. for60 min. Heating source was removed. Ethylene was vented to about 210kPa. The reactor was back filled with 1.4 MPa nitrogen and was releasedto 140 kPa. This was repeated twice. The solution was poured into 300 mLmethanol. The polymer was filtered, washed with 6×50 mL methanol anddried in vacuo. White polymer (19.7 g) was obtained. ¹HNMR in TCE-d₂ at120° C.: 34Me/1000CH₂. Mw=98,991; Mn=35,416(PDI=2.8). Density: 0.902g/cm³. Melt Index: 1.03(190° C). ¹³CNMR(120° C., TCE-d₂): Total Me was29.4(Me=0; Et=10.8; Pr=0.0; Bu=6.0; Hex and higher=11.7).

EXAMPLES 25-30

[0154] In these Examples, all pressures are gauge pressures. Thefollowing transition metal compounds are used in the catalyst systems. Ais an ethylene oligomerization catalyst, while B is an ethylene andα-olefin copolymerization catalyst.

[0155] A is made by methods described in World Patent Application99/02472, while B may be made as described in Ewen, et al., J. Am. Chem.Soc., vol. 110, p. 6255-6256 (1988).

[0156] In these Examples, the following abbreviations are used:

[0157] DSC—differential scanning calorimetry

[0158] GPC—gel permeation chromatography

[0159] MAO—methylaluminoxane

[0160] MAO-IP—an MAO with improved toluene solubility

[0161] MI—melt index

[0162] Mn—number average molecular weight

[0163] Mw—weight average molecular weight

[0164] PE—polyethylene

[0165] PD—Mw/Mn

[0166] RT—room temperature

[0167] TCE—tetrachloroethane

[0168] The DSC was measured at a heating rate of 10° C./min, and themelting points were taken as the peak of the melting endotherm on thesecond heat. ¹³C NMR spectra were taken and interpreted generally asdescribed in World Patent Application 9623010. A Varian Unity® 400 MHzor a Bruker 500 125 MHz spectrometer was used, using a 10 mm probe ontypically 10-15 weight percent polymer solutions. The MI was takenaccording to ASTM method 1238, at a temperature of 190° C., using a 2.16kg weight. Density by IR was determined by melt pressing films 0.2-0.3mm (8-12 mils) in thickness at 180° C. and cooled at approximately 15°C./min. in the press. The IR spectrum of each film was obtained, and thepeak absorbance of the known crystalline band at approx. 1894 cm⁻¹ wasdetermined using a two-point baseline employing minima near 2100 and1850 cm⁻¹. The ratio of this absorbance to film thickness (in mils),termed the infrared crystallinity number (IRCN), was related to densityby a linear calibration. The method was calibrated by measuring the IRCNand gradient tube densities for melt pressed films of 24 commercial PEresins over a range of densities from 0.88 to 0.96. A linear fit to thedata (adjusted r²=0.993) gave the formula: density=6.9707*IRCN+0.8643

EXAMPLE 77

[0169] A 600 mL Parr® reactor was cleaned, heated under vacuum and thenallowed to cool under nitrogen. In a drybox, to a Hoke® cylinder wasadded 5 mL toluene and 4.2 mL MAO(13.5 wt % toluene solution). A (0.12mg in 2 mL toluene) and B (3.5 mg) were mixed with 150 mL2,2,4-trimethyl pentane in a 300 mL RB flask. The flask was capped witha rubber septa. Both the Hoke® cylinder and the flask were brought outof the drybox. Under nitrogen protection, the catalyst solution wascannulated to the reactor. The reactor was pressured with nitrogen andthen the nitrogen pressure was released. The reactor was then pressuredwith ethylene and the ethylene pressure was released. The reactor washeated to 65° C. and was pressurized with 965 kPa ethylene. The MAOsolution was added from the Hoke® cylinder at slightly higher pressure.The ethylene pressure of the reactor was then adjusted to 1.31 MPa. Thereaction mixture was allowed to stir for 25 min. The temperature of thereactor was controlled between 87 to 96° C. Heating source was removed.Ethylene was vented to about 210 kPa. The reactor was back filled with1.38 MPa nitrogen and was vented to 210 kPa. This was done one moretime. The reaction mixture was cooled to RT. The reaction mixture wasthen slowly poured into 400 mL methanol. After stirring at RT for 25min, the polymer was filtered, blended to small pieces, washed withmethanol six times and dried in vacuo. White polymer (24.0 g) wasobtained. ¹HNMR(TCE-d₂, 120° C.): 17Me/1000CH₂. GPC(PE standard, 135°C.): Mw=72,800; Mn=32,400; PD=2.2. Based on DSC, the polymer had twomelting points at 116° C. (14.8 J/g) and 103° C. (108.6 J/g). MI=0.40.

EXAMPLE 78

[0170] The supported catalyst was made by stirring a mixture of B (1.0mg in 1 mL toluene), 54.6 mg 0.1 wt % A in biphenyl, 0.35 g silicasupported MAO (18 wt % Al) and 15 mL toluene. After shaking for 30 min,the solid was filtered, washed with 3×5 mL toluene and dried in vacuofor 1 h. It was then stored in a freezer and was used the same day.

[0171] A 600 mL Parr® reactor was cleaned and was charged with 150 g ofwell baked NaCl. It was dried under full vacuum at 120° C. for 2 h. Itwas then charged with 690 kPa of nitrogen while it was still hot. Awater bath was heated to 85° C. In a drybox, 0.66 mL 13.5 wt % MAO-IPtoluene solution was mixed with 4 mL of toluene. It was transferred to a5 mL gas tight syringe. This was brought out of the drybox and thesolution was injected into the autoclave under positive nitrogenpressure. The mixture was stirred (600 RPM) at 690 kPa nitrogen for 20min. Stirring was stopped. The reactor was then charged with 690 kPa ofnitrogen. In a drybox, 110 mg of freshly made silica supported catalystwas mixed with 4.5 mL cyclohexane. This was transferred to a 5 mL gastight syringe. It was brought out of the drybox. The mixture was theninjected into the autoclave under positive nitrogen pressure. Themixture was then allowed to stir (600 RPM) at 690 kPa nitrogen for 15min. Stirring was stopped. Nitrogen was released to 14 kPa. Theautoclave was evacuated under full vacuum for 15 min, with stirring thelast 5 min. It was recharged with 1.17 MPa nitrogen, then released to 14kPa, and this was repeated. The mixture was allowed to stir at 500 RPM.Ethylene pressure (2.41 MPa) was applied. The reactor was placed in the85° C. water bath. The mixture was allowed to stir at 90° C.-97° C. for2 h. The RT mixture was mixed with 800 mL water. The polymer wasfiltered, washed with water and was blended into pieces with 400 mLwater. It was then filtered, washed with 3×water. The polymer wasblended a few more times, followed by water wash. It was then dried invacuo. White polymer(26.6 g) was obtained. The small amount of leftoveralpha-olefins were extracted using a Soxhlet extractor with hexanes. Thepolymer was then dried in vacuo overnight. Elemental analysis indicatedthat there was no salt (NaCl) left in the polymer. ¹HNMR(TCE-d₂, 120°C.): 20Me/1000CH₂. GPC(PE standard, 135° C.): Mw=92,001; Mn=10,518;PD=8.8. The polymer had a melting point of 126° C. (74 J/g) based onDSC. MI=0.66. The density was 0.919 based on IR.

EXAMPLE 79

[0172] The supported catalyst was made by stirring a mixture of B (1.0mg in 1 mL toluene), 109.2 mg 0.1 wt % A in biphenyl, 0.35 g silicasupported MAO (18wt % Al) and 15 mL toluene. After shaking for 30 min,the solid was filtered, washed with 3×5 mL toluene and dried in vacuofor 1 h. It was then stored in a freezer and was used the same day.

[0173] A 600 mL Parr® reactor was cleaned and was charged with 150 g ofwell baked NaCl. It was dried under full vacuum at 120° C. for 2 h. Itwas then charged with 690 kPa of nitrogen while it was still hot. Awater bath was heated to 90° C. In a drybox, 0.50 mL 13.5 wt % PMAO-IPtoluene solution was mixed with 4 mL of toluene. It was transferred to a5 mL gas tight syringe. This was brought out of the drybox and thesolution was injected to the autoclave under positive nitrogen pressure.The mixture was stirred (600 RPM) at 690 kPa nitrogen for 20 min.Stirring was stopped. In a drybox, 150 mg of freshly made silicasupported catalyst was mixed with 4.5 mL cyclohexane. This wastransferred to a 5 mL gas tight syringe. It was brought out of thedrybox. The mixture was then injected to the autoclave under positivenitrogen pressure. The mixture was then allowed to stir (600 RPM) at 690kPa nitrogen for 15 min. Stirring was stopped. Nitrogen was released to14 kPa. The autoclave was evacuated under full vacuum for 15 min, withstirring the last 5 min. It was recharged with 1.17 MPa nitrogen, thenreleased to 14 kPa, and this was repeated. The mixture was allowed tostir at 500 RPM. Ethylene pressure (2.41 MPa) was applied. The reactorwas placed in the 90° C. water bath. The mixture was allowed to stir at92° C.-95° C. for 1 h, 56 min. Ethylene was then vented. Thepolymer/salt mixture was stirred with 600 mL water for 20 min. Thepolymer was filtered, washed with 3×water. The polymer was blended with400 mL water, filtered, washed with 3×water, then stirred with 500 mLwater for 1 h. This was repeated three times. An AgNO₃ test (for Cl) wasnegative at this point. The polymer was filtered, washed with water andthen dried under full vacuum in a 90° C. oil bath overnight. Whitepolymer (58.1 g) was obtained. The small amounts of leftoveralpha-olefins were extracted using a Soxhlet extractor with hexanes. Thepolymer was then dried in vacuo overnight. Elemental analysis indicatedthat there was no salt (NaCl) left in the polymer. ¹HNMR(TCE-d₂, 120°C.): 19Me/1000CH₂. GPC(PE standard, 135° C.): Mw=104,531; Mn=13,746;PD=7.6. The polymer had two melting points at 125° C. (85.8 J/g) and101° C. (25 J/g) based on DSC. MI=0.96. The density was 0.912 based onIR.

EXAMPLE 80

[0174] The supported catalyst was made by stirring a mixture of B (1.0mg in 1 mL toluene), 54.6 mg 0.1 wt % A in biphenyl, 0.35 g silicasupported MAO (18 wt % Al) and 15 mL toluene. After shaking for 30 min,the solid was filtered, washed with 3×5 mL toluene and dried in vacuofor 1 h. It was then stored in a freezer and was used the same day.

[0175] A 600 mL Parr® reactor was cleaned and was charged with 150 g ofwell baked NaCl. It was dried under full vacuum at 120° C. for 2 h. Itwas then charged with 690 kPa of nitrogen while it was still hot. An oilbath was heated to 85° C. In a drybox, 0.66 mL 13.5 wt % MAO-IP intoluene solution was mixed with 4 mL of toluene. It was transferred to a5 mL syringe. This was brought out of the drybox and the solution wasinjected into the autoclave under positive nitrogen pressure. Themixture was stirred (600 RPM) at 690 kPa nitrogen for 20 min. Stirringwas stopped. In a drybox, 60 mg of freshly made silica supportedcatalyst was mixed with 4.5 mL cyclohexane. This was transferred to a 5mL gas tight syringe. It was brought out of the drybox. The mixture wasthen injected into the autoclave under positive nitrogen pressure. Themixture was then allowed to stir (600 RPM) at 690 kPa nitrogen for 15min. Stirring was stopped. Nitrogen was released to 14 kPa. Theautoclave was evacuated under full vacuum for 15 minutes, with stirringthe last 5 min. It was recharged with 1.17 MPa nitrogen, then releasedto 14 kPa, and this was repeated once. The mixture was allowed to stirat 500 RPM. Ethylene pressure (2.41 MPa) was applied. The reactor wasplaced in the 85° C. oil bath. The mixture was allowed to stir at 75°C.-85° C. for 1 h, then at 110° C.-115° C. for 2 hr. Ethylene wasvented. The polymer/salt mixture was stirred with 600 mL water for 20min. Polymer was filtered, and washed with 3×water. The polymer wasblended with 400 mL water, filtered, washed with 3×water. The polymerwas blended and washed again. It was then dried in vacuo overnight.White polymer (22.7 g) was obtained. ¹HNMR(TCE-d₂, 120° C.):23Me/1000CH₂. GPC(PE standard, 135° C.): Mw=107,173; Mn=25,054; PD=4.3.The polymer had two melting points at 126° C. (32.9 J/g) and 114° C.(50.7 J/g) based on DSC. MI=2.0. The density was 0.919 based on IR.

EXAMPLE 81

[0176] The supported catalyst was made by stirring a mixture of B (0.25mg in 1 mL toluene), 27.2 mg 0.1 wt % A in biphenyl, 0.35 g silicasupported MAO (18 wt % Al) and 15 mL toluene. After shaking for 30 min,the solid was filtered, washed with 3×5 mL toluene and dried in vacuofor 1 h. It was then stored in a freezer and was used the same day.

[0177] A 600 mL Parr® reactor was cleaned and was charged with 150 g ofwell baked NaCl. It was dried under full vacuum at 120° C. for 2 h. Itwas then charged with 690 kPa of nitrogen while it was still hot. Awater bath was heated to 85° C. In a drybox, 0.66 mL 13.5 wt % PMAO-IPin toluene solution was mixed with 4 mL of toluene. It was transferredto a 5 mL syringe. This was brought out of the drybox and the solutionwas injected to the autoclave under positive nitrogen pressure. Themixture was stirred (600 RPM) at 690 kPa nitrogen for 30 min. Stirringwas stopped. In a drybox, 200 mg of freshly made silica supportedcatalyst was mixed with 4.5 mL cyclohexane. This was transferred to a 5mL gas tight syringe. It was brought out of the drybox. The mixture wasthen injected to the autoclave under positive nitrogen pressure. Themixture was then allowed to stir (600 RPM) at 690 kPa nitrogen for 15min. Stirring was stopped. Nitrogen was released to 14 kPa. Theautoclave was evacuated under full vacuum for 15 min, with stirring thelast 5 min. It was recharged with 1.17 MPa nitrogen, then released to 14kPa, and this was repeated once. The mixture was allowed to stir at 500RPM. Ethylene pressure (2.41 kPa) was applied. The reactor was placed inthe 85° C. water bath. The mixture was allowed to stir at 85° C.-93° C.for 2 h. Ethylene was then vented. The polymer/salt mixture was stirredwith 600 mL water for 20 min. Polymer was filtered, washed with 3×water.The polymer was blended with 400 mL water, filtered, and washed with3×water. The polymer was blended, filtered and washed again. It was thendried in vacuo overnight. White polymer (12.7 g) was obtained.¹HNMR(TCE-d₂, 120° C.): 25Me/1000CH₂. GPC(PE standard, 135° C.):Mw=116,721; Mn=43,094; PD=2.7. The polymer had two melting points at122° C. (73.2 J/g) and 91° C. (73.1 J/g) based on DSC. MI=0.42. Thedensity was 0.921 based on IR.

[0178] Using data from the GPC and 13C NMR analyses one can calculate arough K factor for the oligomerization of the ethylene to α-olefin.Based on the Mn, the polymer should have 0.6 ends of chains for each1000 CH₂ groups, so the actual level of Hex+branches in this polymer,excluding ends of chains, is 12.6. Based on 4.4 butyl branches/1000 CH₂groups and 11.5 Hex+branches/1000 CH₂ groups, one can calculate that theK constant was about 0.64. As noted above this calculation is subject toseveral errors and should only be considered approximate.

[0179] Table 11 lists the branching distributions of the above preparedpolymers, as determined by ¹³C NMR. No branches containing odd numbersof carbon atoms were detected. The branching levels for Hex+includeends-of-chains. TABLE 11 Ex. No. 77 78 79 80 81 Et* 6.5 5.4 6.6 4.6 4.9Bu** 3.2 4.1 4.1 4.0 4.4 Hex⁺*** 6.5 9.2 9.7 9.6 13.2  Hex⁺/Bu 2.0 2.22.4 2.4 3.0 Hex⁺/Et 1.0 1.7 1.5 2.1 2.7

EXAMPLE 82

[0180] Rheological measurements were performed on some of the abovepolymers, as well as two comparative polymers. One of these was DuPont2020 polyethylene, a low density polyethylene available from E. I.DuPont de Nemours & Co., Wilmington, De. 19898 U.S.A. The othercomparative polymer was a LLDPE, Exceed® 350D60 available from ExxonChemical., Inc., Houston, Tex., U.S.A., reported to be a copolymer ofethylene and 1-hexene, and to have a density of 0.917 g/cm³. This samplehad an Mw of 112,000, as determined by light scattering.

[0181] A Bohlin CSM rheometer (Bohlin Instruments, Inc., Cranbury, N.J.08512 U.S.A.) was used in the parallel plate mode with 25 mm diameterplates and 1 mm gap to make rheological measurements. Each molded samplewas bathed in a nitrogen atmosphere and measurements were carried out at140° C. after briefly heating to 190° C. to remove any traces ofcrystallinity. Measurements were made in the oscillatory mode between0.001 and 30 Hz. The maximum stress applied was 2000 Pa and thecollected data was always in the linear viscoelastic region. On the samesample, creep/recoil experiments at very low stress (10 Pa) were alsoperformed immediately following the oscillatory flow. Measurements weremade over 19 h to determine melt stability via viscosity and elasticitychanges.

[0182] A special stabilizer package, sample loading and moldingprocedure were used. Ten ml of a stabilizer solution (0.2g each ofIrganox® 1010, Irganox® 1076 and Irgafos® 168 in 100 ml hexane) wassquirted onto 1.2 g of pellets. Following air drying, the sample wasplaced overnight in a vacuum oven at 50° C. with nitrogen bleed. Thepolymer was then loaded into a cold vacuum mold. Vacuum was applied(pressure no greater than 1.3 kPa absolute) to the mold using a gasketto seal against air contamination. The evacuated mold was heated to 140°C., pressure applied followed by a quench cool to RT. Pressure wasreleased at this point and the sample removed from the mold and placedimmediately into the RT rheometer. The sample was then rapidly heated to190° C. (this took about 5 min) then rapidly cooled (another 10 min)back to the measurement temperature prior to trimming, equilibration atthe measurement temperature for about 15 min, and making measurements.The oscillatory flow experiments were performed first; they took about1.5 h. These were followed immediately by the creep/recoil experimentswhich took about 16 additional h. Two identical creep/recoil experimentswere done with 8 ks and 20,000 ks creep and recoil times, respectively.The entire rheometer was bathed in nitrogen and nitrogen was alsoapplied to the rheometer air bearing. Our experience indicates thatsmall amounts of air contamination with hydrocarbon polymers resulted insample degradation. Two separate moldings and measurements were made persample and the results shown are the averaged results shown in FIG. 1.FIG. 1 shows the complex viscosity of the polymers versus frequency ofthe rheometer, which is a measure of shear, higher frequencies beinghigher shear rates. Many of the polymers of the Examples above haveviscosity profiles similar to the DuPont 2020 LDPE, an excellentprocessing polymer.

[0183] Some of these polymers were also analyzed by SEC (same as GPC)and MALS, multiangle light scattering, and at the same time viscometry,to obtain intrinsic viscosity, Mw, and radius of gyration. The weightaveraged molecular weights (Mw) and intrinsic viscosities([η]) weredetermined using a Wyatt Technology (Santa Barbara, Calif. 93117 U.S.A.)Dawn® DSP light scattering photometer and Viscotek (Houston, Tex. 77060U.S.A.) 210R viscometer, respectively. Both of these were connected to aliquid chromatograph (Polymer Laboratories, (Amherst, Mass. 01002U.S.A.) PL210, also called SEC or GPC). Eluent from the SEC is directedto the light scattering instrument through a heated transfer line (alsocontrolled at 150° C.) and then back into the PL210. The oven in thePL210 houses both the differential refractometer and the 210R viscometeras well as the SEC columns. The light scattering instrument employs anAr ion laser at 488 nm. A single dn/dc of −0.100 (mL/g) (determined frommany additional analyses) was used for all calculations. The actualconcentration eluting from the column was determined from the calibrateddifferential refractometer using the dn/dc value of −0.100. In allcases, the integrated concentration was within 2-5% of the weighed massof polymer injected. The solvent used was 1,2,4-trichlorobenzene;stabilized with 0.05% BHT. A temperature of 150° C. was used fordissolution of solutions and for analysis. Solutions were prepared insmall (2 mL) vials at known concentrations of 0.1-0.15%, left in sealedvials in a heating block for 8-12 hours to dissolve, and then analyzed.Polymer solutions were not filtered prior to analysis. Injection volumewas 200 microliters, resulting in the injection of 1-1.5 mg for eachanalysis. Results were obtained using software available from WyattTechnology. The average intrinsic viscosity, [η], was obtained by takingthe ratio of the integrated viscometer peak and the integrateddifferential refractometer peak. Intrinsic viscosity results and Mwvarious polymers are shown in Table 12.

[0184] The results of the Mw and intrinsic viscosity analyses are alsoplotted in FIG. 2, along with the results from other polyethylenes andhydrogenated poly(1,3-butadiene) (PB), a linear polymer which is thesame (after hydrogenation) as polyethylene. It is clear that at a givenMw, many of the polymers used herein have a lower intrinsic viscosity ata given Mw than linear polyethylene or polyethylenes containing onlyshort chain branching (LLDPE). TABLE 12 Polymer S_(T) P_(R) Mw [η]Example 77  86000 1.18 Example 78 ≧0.61 14.4 116000 1.10 Example 79 ≧1.852.6 150000 1.25 Example 80 ≧1.6 52.1 156000 1.19 Example 81 ≧3.8 190193000 1.38 Exxon Exceed ® 350D60 1.00 7.95 112000 1.69 DuPont 2020 LDPE0.19 69.9 278000 1.00

What is claimed is:
 1. A polyethylene having a structural index, S_(T),of about 1.4 or more.
 2. The polyethylene as recited in claim 1 whereinthe structural index is about 2.0 or more.
 3. A polyethylene having aprocessability index, P_(R), of about 40 or more, provided that if astructural index, S_(T), of the polyethylene is less than about 1.4,said polyethylene has fewer than 20 methyl branches per 1000 methylenegroups.
 4. The polyethylene as recited in claim 3 wherein theprocessability index is about 50 or more.
 5. The polyethylene as recitedin claim 3 wherein the processability index is about 100 or more.
 6. Thepolyethylene as recited in claim 3 wherein the structural index is about1.4 or more.
 7. The polyethylene as recited in claim 3 wherein theprocessability index is about 2.0 or more.
 8. A polyethylene which hasat least 2 branches each of ethyl and n-hexyl or longer and at least onen-butyl per 1000 methylene groups, and has fewer than 20 methyl branchesper 1000 methylene groups, and obeys the equation [η]<0.0007 Mw^(0.63)wherein [η] is the intrinsic viscosity of said polyethylene in1,2,4-trichlorbenzene at 150° C. and Mw is the weight average molecularweight.
 9. The polyethylene as recited in claim 8 having a structuralindex, S_(T), of about 1.4 or more.
 10. The polyethylene as recited inclaim 9 wherein the structural index is about 2.0 or more.
 11. Thepolyethylene as recited in claim 8 having a processability index, P_(R),of about 40 or more.
 12. The polyethylene as recited in claim 11 whereinthe processability index is about 50 or more.
 13. The polyethylene asrecited in claim 11 wherein the processability index is about 100 ormore.
 14. The polyethylene as recited in claim 8 having a structuralindex, S_(T), of about 1.4 or more, and a processability index, P_(R),of about 40 or more.
 15. The polyethylene as recited in claim 14 whereinthe structural index is about 2.0 or more.
 16. The polyethylene asrecited in claim 14 wherein the processability index is about 50 ormore.
 17. The polyethylene as recited in claim 16 wherein theprocessability index is about 100 or more.